CN106588618A - Method for catalyzing oxidation of phenol and hydrogen peroxide with selenium-containing catalyst for synthesis of p-benzoquinone - Google Patents
Method for catalyzing oxidation of phenol and hydrogen peroxide with selenium-containing catalyst for synthesis of p-benzoquinone Download PDFInfo
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- CN106588618A CN106588618A CN201610964223.9A CN201610964223A CN106588618A CN 106588618 A CN106588618 A CN 106588618A CN 201610964223 A CN201610964223 A CN 201610964223A CN 106588618 A CN106588618 A CN 106588618A
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- phenol
- hydrogen peroxide
- selenium
- benzoquinone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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Abstract
The invention relates to a method for catalyzing oxidation of phenol and hydrogen peroxide with a selenium-containing catalyst for synthesis of p-benzoquinone. The method is mild in reaction conditions and can be implemented at normal pressure. According to a technical scheme in the invention, the method comprises the following steps: adding phenol, a solvent, the selenium-containing catalyst and hydrogen peroxide into a glass reaction bottle and carrying out a reaction at a certain temperature, wherein analysis results of oxidized liquid show that the conversion rate of phenol is about 30 to 50%, the selectivity of p-benzoquinone is 80 to 90% and resorcinol and ortho-isomers are not produced. High-selectivity preparation of hydroquinone can be realized through hydrogenation reduction of p-benzoquinone.
Description
Technical field
The present invention relates to a kind of method of the Phenol by Hydrogen Peroxide of catalyst containing selenium oxidative synthesis 1,4-benzoquinone.
Background technology
1,4-benzoquinone, yellow crystal.Flammable, 116 DEG C of fusing point, relative density 1.318g/ml is dissolved in ethanol, ether and alkali, micro-
It is dissolved in water.Can distil, its steam is volatile, and decomposed.There is the penetrating odor of similar chlorine.Be a kind of important dyestuff and
Medicine intermediate, for the raw material as manufacture hydroquinone and rubber antioxidant, draws as acrylonitrile and vinyl acetate polymerization
Send out agent and oxidant etc..
The production technology of 1,4-benzoquinone is mainly aniline oxidizing process.Aniline is in H2SO4Jing MnO in medium2Or Na2Cr2O7Oxidation
For 1,4-benzoquinone, the advantage of the method is technical maturity.But the problem that the method is present is that the consumption of pyrolusite is big, in production process
Produce substantial amounts of manganese sulfate, ammonium sulphate waste liquor to be difficult to process, serious environment pollution；On the other hand, acid system has corruption to equipment
Erosion is acted on, and improves production cost.The environmental protection pressure of aniline oxidizing process increasingly increases severely, it will be gradually eliminated.
Recent study personnel begin one's study phenol oxygen or oxygen-containing gas oxidative synthesis 1,4-benzoquinone, such as
CN104557487A, CN104292096A and CN104292095A, there is provided a kind of preparation method of 1,4-benzoquinone compound, with benzene
Phenolic compounds are raw material, and the oxygen used in liquid flux or oxygen-containing gas are sponsored as oxidant in transistion metal compound
Agent and N- replace under hydrocarbon oxy compound or the effect of starlike molecule promoter, and in a mild condition selectivity prepares 1,4-benzoquinone
Compound.This method needs to use high pressure equipment, oxygen pressure to need highest 7.0MPa, equipment is had higher requirements, while using
There is certain security risk in oxygen.CN103420803B, is oxygen source using ozone, equally exists security risk.
Also research worker explores Phenol by Hydrogen Peroxide oxidizing process, such as CN103570506B, using phenol and brucite (catalysis
Agent), hydrogen peroxide is added, but in addition to 1,4-benzoquinone is obtained, there is adjacent benzoquinone in product, the separation for carrying out isomer is needed, subsequently
Process comparatively laborious；
Also research worker is raw material using hydroquinone, synthesizes 1,4-benzoquinone, such as CN104844439A, due to benzene two
The price of phenol differs larger with 1,4-benzoquinone, therefore the method is without economy.
The content of the invention
It is an object of the invention to provide a kind of Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method of catalyst containing selenium, the method
Reaction condition is gentle, and normal pressure is capable of achieving.
Phenol and hydrogen peroxide synthesize hydroquinone under the catalysis of molecular sieve (TS-1), and this is that phenol hydroxylation method synthesizes to benzene
The industrialized producing technology of diphenol, but it is catechol that product has more than half after reaction.Found by screening catalyst, made
Hydrogen peroxide can be catalyzed by phenol high-selectivity oxidation into 1,4-benzoquinone, and not generate Benzodiazepiness, select with a kind of catalyst containing selenium
Property reach as high as 90% or so, and be the 1,4-benzoquinone synthetic route of a brand-new environmental protection without ortho isomer.
The technical scheme for completing foregoing invention task is as follows：By phenol, solvent, selenium catalyst, hydrogen peroxide, input glass is anti-
In answering bottle, react at a certain temperature, the oxidation solution for obtaining by analysis, phenol conversion about 30-50%, 1,4-benzoquinone selectivity
80-90%, generates without Benzodiazepiness and ortho isomer.1,4-benzoquinone can obtaining to benzene two with high selectivity by hydrogenating reduction
Phenol.
Catalyst described in the technical program can be small molecule selenium catalyst, such as benzene seleninic acid, diphenyl disenenide ether,
Two (p-methoxyphenyl) diselenides, dicyclohexyl diselenide, two (N, N- dimethylamino phenyl) diselenides, two (chlorphenyl) two
The selenium catalyst of selenide, dibutyl diselenide etc., or Polymer-supported, such as loaded by polystyrene selenium catalyst (polyphenyl
Ethylene load selenium catalyst preparation process refers to J.Mater.Chem.A, 2016,4,10828-10833)；
Solvent of the present invention can be alcohols, organic nitrile, halogenated hydrocarbons etc., such as methanol, ethanol, isopropanol, positive fourth
Alcohol, dichloroethanes, trichloroethane, acetonitrile etc.；
Catalytic amount is the 0.5-5wt%, preferred 0.2- of phenol quality in oxidation process conditions of the present invention
3wt%；Phenol concentration is 1-40wt%, preferred 5-20wt%；Solvent is 2.5-50 with the mass ratio of phenol：1, preferred 5-15:
1；Hydrogen peroxide concentration is 10-70wt%, preferred 25-50wt%；Hydrogen peroxide is 0.1-7 with the mole ratio of phenol:1, preferably
0.2-5:1；Reaction temperature is 30-100 DEG C, preferred 40-90 DEG C；Response time be 0.5-8 hours, preferred 1-5 hours.Oxidation work
There is material impact in skill condition, these factors are also the technology contents of this method to reaction result.
The technical scheme has the following advantages：
1) process conditions are gentle, and safe, equipment requirements are low.
2) 1,4-benzoquinone can be generated with high selectivity catalysis solution for oxidation of phenol with hydrogen peroxide, and does not generate Benzodiazepiness and ortho position isomery
Body, is the 1,4-benzoquinone synthetic route of a brand-new environmental protection.
3) support type selenium catalyst choice is high, is easily separated with oxidation solution, can reuse at least 5 times, solves
Conventional grained catalyst is difficult to the problem for separating and being easy to run off.
Specific embodiment
The following examples are intended to explain the prominent effect of the present invention, rather than limitation of the invention further.
The preparation process of support type selenium catalyst
In order to better illustrate the preparation technology of support type selenium catalyst, now briefly introduce its preparation process (referring to
J.Mater.Chem.A,2016,4,10828-10833)：Under nitrogen protection, 4g polystyrene resins soak in 30mL cyclohexene
It is wet, tetramethylethylenediamine (37.2mmol, 5.6ml) and n-BuLi (48mmol, 26.7ml) are subsequently adding, stir, it is warming up to
65-70 DEG C, 4hr is reacted, is filtered, filter cake is washed with 30mL THF, filter cake is transferred in reaction flask, add 40ml THF,
0 DEG C is cooled to, dimethyl diselenide ether (5mmol) is added, after stirring 20min, adds 3mL water, polymer to be gradually changed into from brown
Yellow, filters, and filter cake is washed successively with THF, water, methanol, is then dried 24hr in 65 DEG C under vacuum, obtains pure polymer and bears
The first seleno resin of load.
Under nitrogen protection, 4g first seleno resins soak in 60ml chloroforms, and (6mmol is molten to be subsequently adding the chloroformic solution of bromine
In 20mL chloroforms), at 0 DEG C, 30min is stirred, filter, filter cake absolute ethanol washing；Filter cake is transferred in reaction flask,
60ml dehydrated alcohol is added, 2hr is reacted at 70 DEG C, material gradually becomes red, filters, and filter cake is successively with ethanol and dichloromethane
Alkane is washed, and is then dried 24hr in 65 DEG C under vacuum, obtains the Selenium monobromide. resin of the pure Polymer-supporteds of 4.25g.
Under nitrogen protection, 0.7143g Selenium monobromide. resins (1.4mmol/g) soaks in 60ml chloroforms, and at 0 DEG C 10 are added
Equivalent hydrogen peroxide (30wt%), at room temperature, stirs 2hr, and material gradually becomes white, filters, and filter cake uses successively ethanol and two
Chloromethanes are washed, and are then dried 24hr in 65 DEG C under vacuum, obtain pure loaded by polystyrene selenium catalyst (0.6849g,
1.46mmol/g)。
Embodiment 1
Add 1.65g phenol, 11g ethanol, 9.9g 30wt% hydrogen peroxide and 16.5mg benzene sub- in 30ml glass reaction bottles
Selenic acid, under magnetic stirring warming-in-water was to 60 DEG C of insulation reaction 2 hours.Room temperature is down to, 21.5g oxidation solutions, sampling point is obtained
Analysis oxidation solution is constituted, wherein phenol 4.97%, 1,4-benzoquinone 2.58%, as a result phenol conversion 35.24%, 1,4-benzoquinone selectivity
83.03%.
Embodiment 2
1.8g phenol, 10g acetonitriles, 10g 25wt% hydrogen peroxide and 12mg diphenyl two are added in 30ml glass reaction bottles
Selenide, under magnetic stirring warming-in-water was to 70 DEG C of insulation reaction 1.5 hours.Room temperature is down to, 20.4g oxidation solutions are obtained, is sampled
Analysis oxidation solution is constituted, wherein phenol 5.16%, 1,4-benzoquinone 3.59%, as a result phenol conversion 41.52%, 1,4-benzoquinone selectivity
85.29%.
Embodiment 3
1.75g phenol, 9.6g methanol, 8.4g 35wt% hydrogen peroxide and the fourths of 11mg bis- are added in 30ml glass reaction bottles
Base diselenide, under magnetic stirring warming-in-water was to 65 DEG C of insulation reaction 2 hours.Room temperature is down to, 18.2g oxidation solutions are obtained, is taken
Sample analysis oxidation solution is constituted, wherein phenol 5.57%, 1,4-benzoquinone 3.91%, as a result phenol conversion 42.07%, and 1,4-benzoquinone is selected
Property 84.12%.
Embodiment 4
To in 30ml glass reaction bottles add 1.75g phenol, 10.1g dichloroethanes, 9.6g 30wt% hydrogen peroxide and
8.5mg Polymer-supported type selenium catalyst, under magnetic stirring warming-in-water was to 55 DEG C of insulation reaction 2.5 hours.It is down to room temperature,
Catalyst is filtered out, 18.8g oxidation solutions are obtained, sample analysis oxidation solution is constituted, wherein phenol 5.69%, 1,4-benzoquinone 3.84%,
As a result phenol conversion 38.87%, 1,4-benzoquinone selectivity 92.36%.
Embodiment 5-8
On the basis of embodiment 4, Polymer-supported type selenium catalyst is circulated and is applied mechanically, as a result such as following table：
| Embodiment | Catalyst applies mechanically batch | Phenol conversion/% | 1,4-benzoquinone selectivity/% |
| 4 | It is new to throw | 38.87 | 92.36 |
| 5 | Set 1 | 40.05 | 91.68 |
| 6 | Set 2 | 39.42 | 92.31 |
| 7 | Set 3 | 38.57 | 90.58 |
| 8 | Set 4 | 39.48 | 91.27 |
Embodiment 9-12
On the basis of embodiment 1, different selenium catalyst are used instead, investigate catalytic effect, as a result such as following table：
Claims (10)
1. a kind of Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method of catalyst containing selenium, it is characterised in that by phenol, solvent,
Selenium catalyst, hydrogen peroxide, in input glass reaction bottle, react at a certain temperature, obtain the oxidation solution containing 1,4-benzoquinone.
2. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 1, its spy
Levy and be, selenium catalytic amount is the 0.5-5wt% of phenol quality；Phenol concentration is 1-40wt%；Hydrogen peroxide concentration is 10-
70wt%；Hydrogen peroxide is 0.1-7 with the mole ratio of phenol:1；Reaction temperature is 30-100 DEG C；Response time is that 0.5-8 is little
When.
3. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 2, its spy
Levy and be, selenium catalytic amount is the 0.2-3wt% of phenol quality；Phenol concentration is 5-20wt%；Hydrogen peroxide concentration is 25-
50wt%；Hydrogen peroxide is 0.2-5 with the mole ratio of phenol:1；Reaction temperature is 40-90 DEG C；Response time is 1-5 hours.
4. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 1, its spy
Levy and be, described catalyst small molecule selenium catalyst or the selenium catalyst of Polymer-supported.
5. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 4, its spy
Levy and be, the selenium catalyst of described Polymer-supported is loaded by polystyrene selenium catalyst.
6. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 4, its spy
Levy and be, described small molecule selenium catalyst is benzene seleninic acid, diphenyl disenenide ether, two (p-methoxyphenyl) diselenides, bicyclo-
Hexyl diselenide, two (N, N- dimethylamino phenyl) diselenides, two (chlorphenyl) diselenides, dibutyl diselenide.
7. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 1, its spy
Levy and be, described solvent is alcohols, organic nitrile, halogenated hydrocarbon solvent.
8. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 7, its spy
Levy and be, described solvent is methanol, ethanol, isopropanol, n-butyl alcohol, dichloroethanes, trichloroethane, acetonitrile.
9. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 1, its spy
Levy and be, solvent is 2.5-50 with the mass ratio of phenol：1.
10. one kind catalyst containing selenium Phenol by Hydrogen Peroxide oxidative synthesis 1,4-benzoquinone method according to claim 9, its spy
Levy and be, solvent is 5-15 with the mass ratio of phenol:1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109589998A (en) * | 2019-01-15 | 2019-04-09 | 扬州工业职业技术学院 | A kind of novel ZnO/Se/SiO2It the preparation method of composite material and its is applied in preparing phthalide |
| CN109665951A (en) * | 2019-01-15 | 2019-04-23 | 扬州工业职业技术学院 | A kind of ZnO/Se/SiO2Composite material and its application as oxidant |
| CN110102345A (en) * | 2019-05-15 | 2019-08-09 | 扬州大学 | The synthetic method of the catalyst of copolymer containing selenium of catalytic olefin oxidations cracking |
| CN110183318A (en) * | 2019-07-08 | 2019-08-30 | 邵阳学院 | A kind of preparation method of chloranil |
| CN110229053A (en) * | 2019-07-08 | 2019-09-13 | 邵阳学院 | A kind of preparation method of 1,4-benzoquinone |
| CN112275319A (en) * | 2020-11-03 | 2021-01-29 | 扬州工业职业技术学院 | Organic selenium catalyst loaded with carbon nano tube and preparation method and application thereof |
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2016
- 2016-10-28 CN CN201610964223.9A patent/CN106588618B/en active Active
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| RICHARD T. TAYLOR等: "Polystyrene-Bound Phenylseleninic Acid: Catalytic Oxidations of Olefins,Ketones, and Aromatic Systems", 《J. ORG. CHEM.》 * |
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| CN109589998A (en) * | 2019-01-15 | 2019-04-09 | 扬州工业职业技术学院 | A kind of novel ZnO/Se/SiO2It the preparation method of composite material and its is applied in preparing phthalide |
| CN109665951A (en) * | 2019-01-15 | 2019-04-23 | 扬州工业职业技术学院 | A kind of ZnO/Se/SiO2Composite material and its application as oxidant |
| CN109665951B (en) * | 2019-01-15 | 2021-09-03 | 扬州工业职业技术学院 | ZnO/Se/SiO2Composite materials and their use as oxidizers |
| CN109589998B (en) * | 2019-01-15 | 2021-09-03 | 扬州工业职业技术学院 | Novel ZnO/Se/SiO2Preparation method of composite material and application of composite material in preparation of phthalide |
| CN110102345A (en) * | 2019-05-15 | 2019-08-09 | 扬州大学 | The synthetic method of the catalyst of copolymer containing selenium of catalytic olefin oxidations cracking |
| CN110102345B (en) * | 2019-05-15 | 2021-09-10 | 扬州大学 | Synthetic method of selenium-containing copolymer catalyst for catalyzing olefin oxidative cracking |
| CN110183318A (en) * | 2019-07-08 | 2019-08-30 | 邵阳学院 | A kind of preparation method of chloranil |
| CN110229053A (en) * | 2019-07-08 | 2019-09-13 | 邵阳学院 | A kind of preparation method of 1,4-benzoquinone |
| CN112275319A (en) * | 2020-11-03 | 2021-01-29 | 扬州工业职业技术学院 | Organic selenium catalyst loaded with carbon nano tube and preparation method and application thereof |
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